Iron-doped cuprous oxides toward accelerated nonradical oxidation: Doping induced controlled facet transformation and optimized electronic structure

[Display omitted] •Fe-Cu2O were synthesized with controlled facets and doping level.•Fe dopant tailors the local electronic structures of nearby cuprous atoms.•Fe-doping impressively intensifies the performance of PMS activation.•Surface-confined metastable intermediate was identified as the ROS.•The organics was oxidized via an electron-transfer regime. In this study, transition metal-doped and morphology controlled cuprous oxides were synthesized through a facile route and evaluated for bisphenol A (BPA, a model endocrine-disrupting compound) degradation with peroxymonosulfate (PMS). Fe-doped Cu2O exhibited an ultrahigh efficiency for PMS activation and catalytic degradation of BPA. Experimental and computational outcomes illustrate that iron-doping effectively regulated the exposed termination of the oxides and electronic structure of the surrounding copper atoms. Selective radical screening and electron paramagnetic resonance (EPR) spectra witnessed the presence of trace-level free radicals (SO4−, OH and O2−), whereas BPA was primarily oxidized via a nonradical pathway. A surface-confined intermediate (PMS@Fe-Cu2O) was formed via intimate outer-sphere interactions, which exhibited a high oxidizing capacity toward organic substrate via an electron-transfer regime. This study developed atomically engineered cuprous catalysts and provided new mechanistic insights into nonradical oxidation.